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Abstract:

To provide a composition comprising a silsesquioxane compound that is
capable of producing a coating film with excellent heat resistance and
scratch resistance, and that has excellent compatibility with general
polymerizable unsaturated compounds as well as polymerizable unsaturated
compounds with high polarity.
A silsesquioxane compound comprising organic groups each directly
attached to a silicon atom of the compound, at least one of the organic
groups being an organic group having one or more urethane bonds and one
(meth)acryloyloxy group.

Claims:

1. A silsesquioxane compound comprising organic groups each directly
attached to a silicon atom of the compound, at least one of the organic
groups being an organic group having one or more urethane bonds and one
(meth)acryloyloxy group.

2. The silsesquioxane compound according to claim 1 wherein the organic
group having one or more urethane bonds and one (meth)acryloyloxy group
is an organic group represented by the formula (A) below: ##STR00034##
wherein R1 represents a hydrogen atom or a methyl group, R2
represents a C1-10 divalent hydrocarbon group, R3 represents a
C1-10 divalent hydrocarbon group, and Y represents ##STR00035##
wherein R2 is as defined above, and n represents an integer of 0 to
9; ##STR00036## wherein R4 represents a substituted or
unsubstituted C1-6 monovalent hydrocarbon group; or ##STR00037##
wherein R5 represents a substituted or unsubstituted C1-6
monovalent hydrocarbon group.

3. The silsesquioxane compound according to claim 1, wherein the weight
average molecular weight is 1,000 to 100,000.

4. An active energy ray-curable composition comprising the silsesquioxane
compound according to claim 1, and a photoinitiator.

5. The active energy ray-curable composition according to claim 4,
further comprising a polymerizable unsaturated compound.

Description:

TECHNICAL FIELD

[0001] The present invention relates to a silsesquioxane compound having a
polymerizable functional group.

BACKGROUND ART

[0002] Silsesquioxane is a general term for a series of network-like
polysiloxanes with a ladder, cage, or three-dimensional network (random)
structure. Unlike silica, which is a complete inorganic material
represented by general formula SiO2, silsesquioxane is soluble in
general organic solvents; therefore, it is easy to handle, and
processability and moldability during membrane formation etc. are
excellent.

[0003] On the other hand, as an unsaturated compound having radical
polymerization properties, polyfunctional acrylate, unsaturated
polyester, etc., are widely investigated, and are industrially used.
Various studies are conducted on such radical-polymerizable unsaturated
compounds for the purpose of providing scratch resistance, stain
resistance, etc., with their cured products. However, a composition
obtained by mixing an organopolysiloxane compound, such as
silsesquioxane, with a widely used radical-polymerizable unsaturated
compound has disadvantages such that a uniform composition is hard to
produce because of its poor compatibility, and that an organopolysiloxane
compound is separated from the resulting cured product.

[0004] Patent Documents 1 to 5 disclose inventions relating to
silsesquioxane having a radical-polymerizable functional group such as an
acryloyloxy or methacryloyloxy group, and an ultraviolet curable
composition containing the silsesquioxane. Such silsesquioxane-containing
compositions have excellent heat resistance and scratch resistance;
however, silsesquioxane has a problem such that its compatibility with
other polymerizable unsaturated compounds, in particular, with
polymerizable unsaturated compounds having high polarity is insufficient.

[0011] The present invention was made in light of the aforementioned
circumstances.

[0012] An object of the present invention is to provide a silsesquioxane
compound that is capable of producing a coating film with excellent heat
resistance and scratch resistance, and that has excellent compatibility
with general polymerizable unsaturated compounds as well as polymerizable
unsaturated compounds with high polarity.

Solution to Problem

[0013] The present inventors conducted extensive research to solve the
above problems; consequently, they found that the aforementioned problems
can be solved by introducing as an organic group directly attached to a
silicon atom, an organic group having one or more urethane bonds and one
(meth)acryloyloxy group into a silsesquioxane compound. The present
invention was thus accomplished.

Specifically, the present invention is as follows:

Item 1

[0014] A silsesquioxane compound comprising organic groups each directly
attached to a silicon atom of the compound, at least one of the organic
groups being an organic group having one or more urethane bonds and one
(meth)acryloyloxy group.

Item 2

[0015] The silsesquioxane compound according to Item 1, wherein the
organic group having one or more urethane bonds and one (meth)acryloyloxy
group is an organic group represented by the formula (A) below:

[0016] The silsesquioxane compound according to Item 1 or 2, wherein the
weight average molecular weight is 1,000 to 100,000.

Item 4

[0017] An active energy ray-curable composition comprising the
silsesquioxane compound according to any one of Items 1 to 3, and a
photoinitiator.

Item 5

[0018] The active energy ray-curable composition according to Item 4,
further comprising a polymerizable unsaturated compound.

Advantageous Effects of Invention

[0019] The silsesquioxane compound of the present invention can produce a
silsesquioxane compound having excellent compatibility with general
polymerizable unsaturated compounds as well as excellent compatibility
with polymerizable unsaturated compounds having high polarity, by
introducing as an organic group directly attached to a silicon atom, an
organic group having one or more urethane bonds and one (meth)acryloyloxy
group into the silsesquioxane compound.

[0020] Further, because of its excellent compatibility with various
polymerizable unsaturated compounds, the silsesquioxane compound of the
present invention can be used in various active energy ray-curable
compositions, and can improve the heat resistance and scratch resistance
of coating films that are obtained from the active energy ray-curable
compositions.

DESCRIPTION OF EMBODIMENTS

[0021] The silsesquioxane compound of the present invention is a
silsesquioxane compound comprising organic groups each directly attached
to a silicon atom, wherein at least one of the organic groups is an
organic group having one or more urethane bonds and one (meth)acryloyloxy
group (hereinafter, sometimes simply referred to as "the silsesquioxane
compound of the present invention").

[0022] Since at least one of the organic groups directly attached to a
silicon atom in the silsesquioxane compound of the present invention is
an organic group having one or more urethane bonds and one
(meth)acryloyloxy group, the silsesquioxane compound has excellent
compatibility with various polymerizable unsaturated compounds because of
the polarity of the urethane bond(s) included in the organic group, and
the silsesquioxane compound can be cured by active energy ray irradiation
in the presence of a photoinitiator because of the (meth)acryloyloxy
group included in the organic group.

[0023] For this reason, the silsesquioxane compound of the present
invention is useable in various active energy ray-curable compositions.

Silsesquioxane Compound of the Present Invention

[0024] The silsesquioxane compound of the present invention has organic
groups each directly attached to a silicon atom, in which at least one of
the organic groups directly attached to a silicon atom is an organic
group having one or more urethane bonds and one (meth)acryloyloxy group.

[0025] The term "silsesquioxane compound" used herein indicates not only a
silsesquioxane compound having a structure in which all of the Si--OH
groups (hydroxy silyl groups) are hydrolyzed and condensed, but also
silsesquioxane compounds having a rudder structure, an incomplete cage
structure, or a random structure, in which Si--OH groups remain.

[0026] In the silsesquioxane compound of the present invention, the
proportion of the silsesquioxane compound having a structure in which all
of the Si--OH groups are hydrolyzed and condensed is preferably 80 mass %
or more, more preferably 90 mass % or more, and even more preferably 100
mass % or more in terms of liquid stability.

[0027] An example of the silsesquioxane compound of the present invention
is a silsesquioxane compound in which an organic group having one or more
urethane bonds and one (meth)acryloyloxy group is represented by the
formula (A) below:

[0030] The silsesquioxane compound of the present invention may include,
among the organic groups represented by the formula (A) above, one kind
of organic group, or two or more kinds of organic groups.

[0031] In other words, examples of the silsesquioxane compound of the
present invention include a silsesquioxane compound in which an organic
group having one or more urethane bonds and one (meth)acryloyloxy group
is at least one member selected from the group consisting of organic
groups represented by the formulae (I) to (III) below:

wherein R1 to R3 are as defined above, and R4 represents a
substituted or unsubstituted C1-6 monovalent hydrocarbon group; or

##STR00011##

wherein R1 to R3 are as defined above, and R5 represents a
substituted or unsubstituted C1-6 monovalent hydrocarbon group.

[0032] R2 is not particular limited as long as it represents a
C1-10 divalent hydrocarbon group. Specific examples thereof include
alkylene groups such as methylene, ethylene, 1,2-propylene,
1,3-propylene, 1,2-butylene, 1,4-butylene, and hexylene; cyclo alkylene
groups such as cyclohexylene; arylene groups such as phenylene, xylylene,
and biphenylene; and the like. Of these, C1-6 divalent hydrocarbon
groups, in particular, ethylene, 1,2-propylene, and 1,4-butylene are
preferred because they have superior heat resistance, scratch resistance,
and compatibility with polymerizable unsaturated compounds having high
polarity.

[0033] R3 is not particularly limited as long as it represents a
C1-10 divalent hydrocarbon group. Specific examples thereof include
alkylene groups such as methylene, ethylene, 1,2-propylene,
1,3-propylene, 1,2-butylene, 1,4-butylene, and hexylene; cyclo alkylene
groups such as cyclohexylene; arylene groups such as phenylene, xylylene,
and biphenylene; and the like. Of these, C1-6 divalent hydrocarbon
groups, in particular, ethylene and 1,3-propylene are preferred because
they have superior heat resistance, scratch resistance, and compatibility
with polymerizable unsaturated compounds having high polarity.

[0034] n is not particularly limited as long as it is an integer of 0 to
9. n is preferably an integer of 0 to 5, more preferably 0 to 3, and most
preferably 0 or 1.

[0035] R4 is not particularly limited as long as it is a substituted
or unsubstituted C1-6 monovalent hydrocarbon group. Specific
examples include monovalent acyclic aliphatic hydrocarbon groups or
monovalent cyclic aliphatic hydrocarbon groups such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl,
isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, and
other straight or branched alkyl groups; trifluoromethyl,
3,3,3-trifluoro-n-propyl, and other fluorine-containing alkyl groups.
Methyl is particularly preferred since it has excellent compatibility
with a polymerizable unsaturated compound having high polarity.

[0036] R5 is not particularly limited as long as it is a substituted
or unsubstituted C1-6 monovalent hydrocarbon group. Specific
examples include monovalent acyclic aliphatic hydrocarbon groups or
monovalent cyclic aliphatic hydrocarbon groups such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl,
isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, and
other straight or branched alkyl groups; trifluoromethyl,
3,3,3-trifluoro-n-propyl, and other fluorine-containing alkyl groups.
Methyl is particularly preferred since it has excellent compatibility
with a polymerizable unsaturated compound having high polarity.

[0037] The organic group represented by the formula (I) is preferably an
organic group in which R1 is a hydrogen atom, R2 is an ethylene
group or a 1,4-butylene group, R3 is an ethylene group or a
1,3-propylene group, and n is 0 because it has superior heat resistance,
scratch resistance, compatibility with a polymerizable unsaturated
compound having high polarity, and active energy-ray curability.

[0038] The organic group represented by the formula (II) is preferably an
organic group in which R4 is a methyl group, R3 is an ethylene
group or a 1,3-propylene group, R1 is a hydrogen atom, and R2
is an ethylene group because it has superior heat resistance, scratch
resistance, compatibility with polymerizable unsaturated compounds having
high polarity and active energy-ray curability.

[0039] The organic group represented by the formula (III) is preferably an
organic group in which R5 is a methyl group, R3 is an ethylene
group or a 1,3-propylene group, R1 is a hydrogen atom, and R2
is an ethylene group because it has superior heat resistance, scratch
resistance, compatibility with polymerizable unsaturated compounds having
high polarity and active energy-ray curability.

[0040] The silsesquioxane compound of the present invention may have a
single composition or a mixture of compounds having different
compositions.

[0041] The weight average molecular weight of the silsesquioxane compound
of the present invention is not particularly limited. The weight average
molecular weight is preferably 1,000 to 100,000, and more preferably
1,000 to 10,000. These ranges are significant in terms of the heat
resistance of coating films obtained from the silsesquioxane compound of
the present invention, and the viscosity and application properties of
active energy ray-curable compositions comprising the silsesquioxane
compound of the present invention.

[0042] In the present specification, the weight average molecular weight
is a value determined by converting the weight average molecular weight
measured by gel permeation chromatography ("HLC8120GPC" produced by Tosoh
Corporation), based on the weight average molecular weight of
polystyrene. Measurements were conducted using the four columns "TSKgel
G-4000 HXL", "TSKgel G-3000 HXL", "TSKgel G-2500 HXL" and "TSKgel G-2000
HXL" (trade names; produced by Tosoh Corporation) under the following
conditions: mobile phase: tetrahydrofuran; measurement temperature:
40° C.; flow rate: 1 ml/min.; and detector: R1.

Method of Producing Silsesquioxane Compound of the Present Invention

[0043] The silsesquioxane compound of the present invention may be
produced by various methods. For example, the compound may be produced by
the method shown in the following production method A or B.

Production Method A

[0044] For example, the production method A is carried out using a
starting material containing a hydrolyzable silane having an organic
group that is directly attached to a silicon atom and has one or more
urethane bonds and one (meth)acryloyloxy group.

[0045] Specifically, the silsesquioxane compound of the present invention
is produced, for example, by hydrolysis condensation of the starting
material using a hydrolyzable silane represented by the formula (IV)
below, and optionally, a hydrolyzable silane other than the hydrolyzable
silane represented by the formula (IV) below, in the presence of a
catalyst.

R6SiX3 (IV)

[0046] R6 in the formula (IV) is an organic group having one or more
urethane bonds and one (meth)acryloyloxy group. X is the same or
different, and each represents chlorine or a C1-6 alkoxy group.

[0049] Hydrolyzable silanes other than those represented by the formula
(IV) are not particularly limited as long as they are capable of
producing a silsesquioxane compound through hydrolysis condensation with
the hydrolyzable silane represented by the formula (IV). Specific
examples thereof include methyltrimethoxysilane, methyltriethoxysilane,
ethyltrimethoxysilane, ethyltriethoxysilane, and like
alkyltrialkoxysilanes.

[0050] The hydrolyzable silane represented by the formula (IV) can be
obtained by reacting, for example, isocyanate-containing trialkoxysilane
and hydroxy-containing (meth)acrylic acid ester.

[0051] Specific examples of hydrolyzable silanes represented by the
formula (IV) include those represented by the formula (V):

##STR00012##

wherein R1, R2, R3, n, and X are as defined above.

[0052] The hydrolyzable silane represented by the formula (V) can be
obtained by reacting, for example, a hydrolyzable silane represented by
the formula (VI) and a compound represented by the formula (VII):

##STR00013##

wherein R3 and X are as defined above, and

##STR00014##

wherein R1, R2, and n are as defined above.

[0053] Examples of compounds represented by the formula (VI) include
3-isocyanate propyltrimethoxysilane, 3-isocyanatepropyl triethoxysilane,
and the like.

[0055] The reaction of the hydrolyzable silane represented by the formula
(VI) and the compound represented by the formula (VII) can be performed
according to an ordinary method of reacting an isocyanate group and a
hydroxy group.

[0056] The proportion of the hydrolyzable silane represented by the
formula (VI) and the compound represented by the formula (VII) used in
the above reaction scheme is such that the latter is about 0.90 to about
1.10 mol, and preferably about 0.95 to about 1.05 mol, per mol of the
former.

[0057] The reaction temperature is 0 to 200° C., preferably 20 to
200° C., and more preferably 20 to 120° C. The reaction can
be performed at any pressure; however, the pressure is preferably in the
range of 0.02 to 0.2 MPa, and particularly, 0.08 to 0.15 MPa. The
reaction usually completes in about 2 to about 10 hours.

[0058] In the reaction, catalysts may be suitably used. Examples of
catalysts include tertiary amines such as triethylamine, organic metal
compounds such as dibutyltin dilaurate, and the like.

[0060] Examples of hydrolyzable silanes other than those represented by
the formula (IV) include hydrolyzable silanes represented by the formula
(VIII) or (IX):

##STR00015##

wherein R1, R2, R3, R4, and X are as defined above,
and

##STR00016##

wherein R1, R2, R3, R5, and X are as defined above.

[0061] The hydrolyzable silane represented by the formula (VIII) can be
obtained, for example, by reacting a hydrolyzable silane represented by
the formula (X) with a compound represented by the formula (XI), thereby
yielding a product, and by further reacting a compound represented by the
formula (XII) with the product:

##STR00017##

wherein R3 and X are as defined above,

##STR00018##

wherein R4 is as defined above, and

##STR00019##

wherein R1 and R2 are as defined above.

[0062] Examples of hydrolyzable silanes represented by the formula (X)
include 3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropyltriethoxysilane, and the like.

[0065] The hydrolyzable silane represented by the formula (IX) can be
obtained, for example, by reacting a hydrolyzable silane represented by
the formula (XIII) with a compound represented by the formula (XIV),
thereby yielding a product, and by further reacting a compound
represented by the formula (XV) with the product:

##STR00020##

wherein R3 and X are as defined above,

##STR00021##

wherein R5 is as defined above, and

##STR00022##

wherein R1 and R2 are as defined above.

[0066] Examples of hydrolyzable silanes represented by the formula (XIII)
include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and the like.

[0067] As the compound represented by the formula (XIV), compounds listed
in the description of the compound represented by the formula (XI) can be
used.

[0068] As the compound represented by the formula (XV), compounds listed
in the description of the compound represented by the formula (XII) can
be used.

[0069] The reaction of the hydrolyzable silane represented by the formula
(X) and the compound represented by the formula (XI), and the reaction of
the hydrolyzable silane represented by the formula (XIII) and the
compound represented by the formula (XIV) can be carried out according to
an ordinary method of reacting a carboxy group and an epoxy group.

[0070] The proportion of the hydrolyzable silane represented by the
formula (X) and the compound represented by the formula (XI) used in the
reaction is such that the latter is about 0.80 to about 1.20 mol, and
preferably about 0.90 to about 1.10 mol, per mol of the former.

[0071] The proportion of the compound represented by the formula (XIII)
and the compound represented by the formula (XIV) is such that the latter
is about 0.80 to about 1.20 mol, and preferably about 0.90 to about 1.10
mol, per mol of the former.

[0072] The reaction temperature is, for example, 0 to 200° C.,
preferably 20 to 200° C., and more preferably 20 to 120° C.
The reaction generally completes in about 10 to about 24 hours.

[0073] In the reaction, catalysts may be used. Specific examples of
catalysts include tertiary amines such as triethylamine and
benzyldimethylamine; quaternary ammonium salts such as
tetramethylammonium chloride, tetraethylammonium bromide, and
tetrabutylammonium bromide; secondary amine salts such as acetate and
formate of diethylamine etc.; alkali metal or alkaline earth metal
hydroxides such as sodium hydroxide and calcium hydroxide; alkali metal
or alkaline earth metal salts such as sodium acetate and calcium acetate;
imidazoles; cyclic nitrogen-containing compounds such as
diazabicycloundecene; phosphorus compounds such as triphenylphosphine and
tributylphosphine; and the like. The amount of the catalyst used is not
limited, but is specifically, for example, 0.01 to 5 mass % based on the
amount of the reaction starting material.

[0075] The reaction of the compound represented by the formula (XII) with
the reaction product (hereinafter sometimes simply referred to as
reaction product (X-XI)) that is obtained by reacting the hydrolyzable
silane represented by the formula (X) and the compound represented by the
formula (XI), and the reaction of the compound represented by the formula
(XV) with the reaction product (hereinafter sometimes simply referred to
as reaction product (XIII-XIV)) that is obtained by reacting the
hydrolyzable silane represented by the formula (XIII) and the compound
represented by the formula (XIV) can be carried out according to an
ordinary method of reacting a hydrolyzable group and an isocyanate group.

[0076] The proportion of the reaction product (X-XI) and the compound
represented by the formula (XII) used in the above reaction is such that
the latter is about 0.90 to about 1.10 mol, and preferably about 0.95 to
about 1.05 mol, per mol of the former.

[0077] The proportion of the reaction product (XIII-XIV) and the compound
represented by the formula (XV) used in the above reaction is such that
the latter is about 0.90 to about 1.10 mol, and preferably about 0.95 to
about 1.05 mol, per mol of the former.

[0078] The reaction temperature is, for example, 0 to 200° C.,
preferably 20 to 200° C., and more preferably 20 to 120° C.
The reaction can be carried out at any pressure; however, the pressure is
preferably in the range of 0.02 to 0.2 MPa, and more preferably in the
range of 0.08 to 0.15 MPa. The reaction generally completes in about 2 to
about 10 hours.

[0079] In the reaction, catalysts may be suitably used. Examples of the
catalysts include tertiary amines such as triethylamine; organic metal
compounds such as dibutyltin dilaurate; and the like.

[0081] In the method of producing the invention, the silsesquioxane
compound of the present invention is specifically obtained as follows:

[0082] [1] The hydrolyzable silane represented by the formula (IV) is used
as a starting material and subjected to hydrolysis condensation in the
presence of a catalyst, or

[0083] [2] the hydrolyzable silane represented by the formula (IV) and
other hydrolyzable silanes are used as starting materials and subjected
to hydrolysis condensation in the presence of a catalyst.

[0084] As the catalyst, a basic catalyst is preferably used. Specific
examples of basic catalysts include alkali metal hydroxides such as
potassium hydroxide, sodium hydroxide, and cesium hydroxide; ammonium
hydroxide salts such as tetramethylammonium hydroxide, tetraethylammonium
hydroxide, tetrabutylammonium hydroxide, and benzyl trimethylammonium
hydroxide; ammonium fluoride salts such as tetrabutylammonium fluoride;
and the like.

[0085] Although the amount of the catalyst used is not limited, using an
overly large amount of the catalyst results in high costs, and
difficulties in removing the catalyst, while using an overly small amount
of the catalyst slows the reaction. Therefore, the amount of the catalyst
is preferably 0.0001 to 1.0 mol, and more preferably 0.0005 to 0.1 mol,
per mol of hydrolyzable silane.

[0086] When the hydrolysis condensation reaction is carried out (the above
process [1] or [2]), water is used. The proportion of hydrolyzable silane
to water is not limited. The amount of water used is preferably 0.1 to
100 mol, and more preferably 0.5 to 3 mol, per mol of hydrolyzable
silane. When the amount of water is too low, the reaction proceeds
slowly, possibly resulting in a reduced yield of the target
silsesquioxane compound. Conversely, when the amount of water is too
high, the molecular weight of the resulting product is increased,
possibly resulting in a reduced amount of product having the desired
structure. Moreover, when a basic catalyst is used in the form of an
aqueous solution, the water used in the reaction may be substituted by
the solution, or water may be further added.

[0087] In the above hydrolysis condensation reaction, an organic solvent
may or may not be used. The use of an organic solvent is preferred in
terms of preventing gelation and controlling viscosity during production.
As the organic solvent, a polar organic solvent and a nonpolar organic
solvent may be used alone or as a mixture thereof.

[0088] Examples of polar organic solvents include lower alcohols such as
methanol, ethanol, and 2-propanol; ketones such as acetone, and methyl
isobutyl ketone; and ethers such as tetrahydrofuran. Particularly,
acetone and tetrahydrofuran are preferred because they have a low boiling
point, and their use results in a homogeneous system and improved
reactivity. Preferred examples of nonpolar organic solvents include
hydrocarbon-based solvents; toluene, xylene, and like organic solvents
that have a boiling point higher than that of water are more preferred;
and toluene and like organic solvents that are azeotroped with water are
particularly preferred because water can be efficiently removed from the
system. Particularly, a mixture of a polar organic solvent and a nonpolar
organic solvent is preferably used because the aforementioned advantages
of both solvents can be achieved.

[0089] The temperature in the hydrolysis condensation reaction is 0 to
200° C., preferably 10 to 200° C., and more preferably 10
to 120° C. Although this reaction can be carried out at any
pressure, the pressure is preferably in the range of 0.02 to 0.2 MPa, and
more preferably in the range of 0.08 to 0.15 MPa. The reaction usually
completes in about 1 to about 12 hours.

[0090] In the hydrolysis condensation reaction, the condensation reaction
proceeds with the hydrolysis reaction. In terms of liquid stability, it
is preferred that most of the hydrolyzable groups in the hydrolyzable
silane (for example, Xs in the formula (IV)), and preferably 100% of the
Xs, are hydrolyzed into hydroxyl groups (OH groups), and that most of the
OH groups, preferably 80% or higher, more preferably 90% or higher, and
even more preferably 100% of the OH groups, are condensed.

[0091] After the hydrolysis condensation reaction, the solvent, alcohol
produced by the reaction, and catalyst may be removed from the mixture by
a known technique. The obtained product may be further purified by
removing the catalyst using various purification methods (e.g., washing,
column separation, and solid absorbent), depending on the purpose.
Preferably, in terms of efficiency, the catalyst is removed by washing
with water.

[0092] The silsesquioxane compound of the present invention is produced by
the above-described production method.

[0093] When not all of the OH groups are condensed in the hydrolysis
condensation reaction, the product obtained by the production method of
the present invention may contain, other than the silsesquioxane compound
having a structure in which all of the Si--OH (hydroxysilyl) groups have
been subjected to hydrolysis condensation, silsesquioxane compounds
having a rudder structure, an incomplete cage structure, and/or a random
structure, in which the Si--OH groups remain. The silsesquioxane compound
of the present invention obtained by the production method of the present
invention may contain such compounds having a rudder structure, an
incomplete cage structure, and/or a random structure.

Production Method B

[0094] For example, the production method B comprises step B1 of producing
a silsesquioxane compound having an epoxy group using a hydrolyzable
silane having an epoxy group, step B2 of reacting the carboxyl group of a
compound having a carboxyl group with the epoxy group contained in the
silsesquioxane compound obtained in step B1, thereby producing a
silsesquioxane compound having a secondary hydroxyl group, and step B3 of
reacting the isocyanate group of a compound having a (meth)acryloyloxy
group and an isocyanate group with the secondary hydroxy group in the
silsesquioxane compound obtained in step B2.

Step B1

[0095] Examples of epoxy group-containing hydrolyzable silanes used in
step B1 include hydrolyzable silanes represented by the formula (XVI) or
(XVII) below.

##STR00023##

In the formulae (XVI) and (XVII), R3 and X are as defined above.

[0096] In step B1, a silsesquioxane compound having an epoxy group is
specifically obtained as follows:

[3] The hydrolyzable silanes represented by the formula (XVI) and/or the
formula (XVII) are used as starting materials, and subjected to
hydrolysis condensation in the presence of a catalyst; or [4] The
hydrolyzable silanes represented by the formula (XVI) and/or the formula
(XVII), and hydrolyzable silanes other than those having an epoxy group
are subjected to hydrolysis condensation in the presence of a catalyst.

[0097] Hydrolyzable silanes other than the aforementioned epoxy
group-containing hydrolyzable silanes are not particularly limited as
long as they are capable of producing a silsesquioxane compound through
hydrolysis condensation with an epoxy group-containing hydrolyzable
silane. Specific examples thereof include alkyltrialkoxysilanes such as
methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane,
ethyltriethoxysilane, and the like.

[0098] As the catalyst, a basic catalyst is preferably used. Specific
examples of basic catalysts include alkali metal hydroxides such as
potassium hydroxide, sodium hydroxide, and cesium hydroxide; ammonium
hydroxide salts such as tetramethylammonium hydroxide, tetraethylammonium
hydroxide, tetrabutylammonium hydroxide, and benzyl trimethylammonium
hydroxide; ammonium fluoride salts such as tetrabutylammonium fluoride;
and the like.

[0099] Although the amount of the catalyst used is not limited, using an
overly large amount of the catalyst results in high costs and
difficulties in removing the catalyst, while using an overly small amount
of the catalyst slows the reaction. Therefore, the amount of the catalyst
used is preferably 0.0001 to 1.0 mol, and more preferably 0.0005 to 0.1
mol, per mol of hydrolyzable silane.

[0100] When the hydrolysis condensation reaction is carried out (the above
process [3] or [4]), water is used. The proportion of hydrolyzable silane
and water is not particularly limited. The amount of water used is
preferably 0.1 to 100 mol, and more preferably 1.5 to 3 mol, per mol of
hydrolyzable silane. When the amount of water is too low, the reaction
proceeds slowly, possibly resulting in a reduced yield of the target
silsesquioxane. Conversely, when the amount of water is too high, the
molecular weight of the resulting product is increased, possibly
resulting in a reduced amount of product having the desired structure.
Moreover, when a basic catalyst is used in the form of an aqueous
solution, the water used in the reaction may be substituted by the
solution, or water may be further added.

[0101] In the above hydrolysis condensation reaction, an organic solvent
may or may not be used. The use of an organic solvent is preferred in
terms of preventing gelation and controlling viscosity during production.
As the organic solvent, a polar organic solvent and a nonpolar organic
solvent may be used alone or as a mixture thereof.

[0102] Examples of polar organic solvents include lower alcohols such as
methanol, ethanol, and 2-propanol; ketones such as acetone and methyl
isobutyl ketone; and ethers such as tetrahydrofuran. Particularly,
acetone and tetrahydrofuran are preferred because they have a low boiling
point, and the use thereof results in a homogeneous system and improved
reactivity. Preferred examples of nonpolar organic solvents include
hydrocarbon-based solvents; toluene, xylene, and like organic solvents
that have a boiling point higher than that of water are more preferred;
and toluene and like organic solvents that are azeotroped with water are
particularly preferred because water can be efficiently removed from the
system. Particularly, a mixture of a polar organic solvent and a nonpolar
organic solvent is preferably used because the aforementioned advantages
of both solvents can be achieved.

[0103] The temperature in the hydrolysis condensation reaction is 0 to
200° C., preferably 10 to 200° C., and more preferably 10
to 120° C. The reaction usually completes in about 1 to about 12
hours.

[0104] In the hydrolysis condensation reaction, the condensation reaction
proceeds with the hydrolysis reaction. In terms of liquid stability, it
is preferred that most of the Xs in the formulae (XVI) or (XVII), and
preferably 100% of the Xs, are hydrolyzed into hydroxyl (OH) groups, and
that most of the OH groups, preferably 80% or higher, more preferably 90%
or higher, and even more preferably 100% of the OH groups, are condensed.

Step B2

[0105] In step B2, a silsesquioxane compound that has organic groups
represented by the formula (XX) as organic groups directly attached to a
silicon atom is produced by reacting a compound represented by the
formula (XIX) with the silsesquioxane compound obtained in step B1 that
has organic groups represented by the formula (XVIII) as organic groups
directly attached to a silicon atom.

##STR00024##

[0106] In the formulae (XVIII), (XIX), and (XX), R3 and R4 are
as defined above.

[0107] As another example, a silsesquioxane compound that has organic
groups represented by the formula (XXIII) as organic groups directly
attached to a silicon atom is produced by reacting a compound represented
by the formula (XXII) with the silsesquioxane compound obtained in step
B1 that has organic groups represented by the formula (XXI) as organic
groups directly attached to a silicon atom.

##STR00025##

[0108] In the formulae (XXI), (XXII), and (XXIII), R3 and R5 are
as defined above.

[0109] The reaction for producing the silsesquioxane compound that has an
organic group represented by the formula (XX) as an organic group
directly attached to a silicon atom, and the reaction for producing the
silsesquioxane compound that has an organic group represented by the
formula (XXIII) as an organic group directly attached to a silicon atom
can be carried out according to an ordinary method of reacting an epoxy
group and a carboxyl group.

[0110] The reaction temperature is 0 to 200° C., preferably 20 to
200° C., and more preferably 20 to 120° C. The reaction
usually completes in about 10 to about 24 hours.

[0111] In the above reaction, the proportion of the compound represented
by the formula (XIX) and the silsesquioxane compound including the
organic group represented by the formula (XVIII) is such that the
compound represented by the formula (XIX) is contained in an amount of
about 0.80 to about 1.20 mol, and preferably about 0.90 to about 1.10
mol, per mol of the organic group represented by the formula (XVIII) in
the silsesquioxane compound.

[0112] In the above reaction, the proportion of the compound represented
by the formula (XXII) and the silsesquioxane compound including the
organic group represented by the formula (XXI) is such that the compound
represented by the formula (XXII) is contained in an amount of about 0.80
to about 1.20 mol, and preferably about 0.80 to about 1.20 mol, per mol
of the organic group represented by the formula (XXI) in the
silsesquioxane compound.

[0113] In the reaction, catalysts may be suitably used. Specific examples
of catalysts include tertiary amines such as triethylamine and
benzyldimethylamine; quaternary ammonium salts such as
tetramethylammonium chloride, tetraethylammonium bromide, and
tetrabutylammonium bromide; secondary amine salts such as acetate and
formate of diethylamine etc.; alkali metal or alkaline earth metal
hydroxides such as sodium hydroxide and calcium hydroxide; alkali metal
or alkaline earth metal salts such as sodium acetate and calcium acetate;
imidazoles; cyclic nitrogen-containing compounds such as
diazabicycloundecene; phosphorus compounds such as triphenylphosphine and
tributylphosphine; and the like. The amount of the catalyst used is not
limited, but is specifically, for example, 0.01 to 5 mass % based on the
amount of the reaction starting material.

[0115] In step B3, a compound represented by the formula (XXIV) is reacted
with the silsesquioxane compound obtained in step B2 that has the organic
group represented by the formula (XX) as an organic group directly
attached to a silicon atom.

##STR00026##

In the formula (XXIV), R1 and R2 are as defined above.

[0116] By this reaction, the silsesquioxane compound that has organic
groups represented by the formula (II) as organic groups directly
attached to a silicon atom can be obtained.

[0117] As another example, the compound represented by the formula (XXV)
is reacted with the silsesquioxane compound obtained in step B2 that has
organic groups represented by the formula (XXIII) as organic groups
directly attached to a silicon atom.

##STR00027##

In the formula (XXV), R1 and R2 are as defined above.

[0118] By this reaction, a silsesquioxane compound having an organic group
represented by the formula (III) as an organic group directly attached to
a silicon atom can be obtained.

[0119] The reaction can be carried out according to an ordinary method of
reacting a hydroxyl group and an isocyanate group. The reaction
temperature is 0 to 200° C., preferably 10 to 200° C., and
more preferably 10 to 120° C. The reaction usually completes in
about 2 to about 10 hours.

[0120] In the reaction, the proportion of the compound represented by the
formula (XXIV) and the silsesquioxane compound including the organic
group represented by the formula (XX) is such that the compound
represented by the formula (XXIV) is contained in an amount of about 0.90
to about 1.10 mol, and preferably about 0.95 to about 1.05 mol, per mol
of the organic group represented by the formula (XX) in the
silsesquioxane compound.

[0121] In the reaction, the proportion of the compound represented by the
formula (XXV) and the silsesquioxane compound including the organic group
represented by the formula (XXIII) is such that the compound represented
by the formula (XXV) is contained in an amount of about 0.90 to about
1.10 mol, and preferably about 0.95 to about 1.05 mol, per mol of the
organic group represented by the formula (XXIII) in the silsesquioxane
compound.

[0122] In the reaction, catalysts may be suitably used. Examples of
catalysts include tertiary amines such as triethylamine; organic metal
compounds such as dibutyltin dilaurate; and the like.

[0123] The silsesquioxane compound of the present invention can be
produced according to the production method described above.

[0124] The target compound obtained by the aforementioned reaction is
separated from the system by general separation means, and can be further
purified. Separation and purification are performed, for example, by way
of evaporation, solvent extraction, dilution, recrystallization, column
chromatography, ion-exchange chromatography, gel chromatography, affinity
chromatography, etc.

[0125] When not all of the OH groups are condensed in the hydrolysis
condensation reaction in step B1, the product obtained by the production
method B may contain, other than a silsesquioxane compound having a
structure in which all of the Si--OH groups are subjected to hydrolysis
condensation, silsesquioxane compounds having a rudder structure, an
incomplete cage structure, and/or a random structure, in which the Si--OH
groups remain. The silsesquioxane compound of the present invention
obtained by the production method B may contain such compounds having a
rudder structure, an incomplete cage structure, and/or a random
structure.

Active Energy Ray-Curable Composition

[0126] The active energy ray-curable composition of the present invention
comprises the silsesquioxane compound of the present invention and a
photoinitiator.

Photoinitiator

[0127] There is no particular limitation to the usable photoinitiators, as
long as they absorb an active energy ray and generate a radical.

[0128] Examples of the photoinitiators include benzyl, diacetyl, and like
α-diketones; benzoin and like acyloins; benzoin methyl ether,
benzoin ethyl ether, benzoin isopropyl ether, and like acyloin ethers;
thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone,
thioxanthone-4-sulfonic acid, and like thioxanthones; benzophenone,
4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone,
and like benzophenones; Michler's ketones; acetophenone,
2-(4-toluenesulfonyloxy)-2-phenylacetophenone,
p-dimethylaminoacetophenone,
α,α'-dimethoxyacetoxybenzophenone,
2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone,
2-methyl[4-(methylthio)phenyl]-2-morpholino-1-propanone,
2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one,
α-isohydroxy isobutylphenone,
α,α'-dichloro-4-phenoxyacetophenone,
1-hydroxy-cyclohexyl-phenyl-ketone, and like acetophenones;
2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(acyl)phosphine oxide,
and like acylphosphine oxides; anthraquinone, 1,4-naphthoquinone, and
like quinones; phenacyl chloride, trihalomethylphenylsulfone,
tris(trihalomethyl)-s-triazine, and like halogenated compounds;
di-t-butyl peroxide, and like peroxides; etc. These may be used singly,
or in a combination of two or more.

[0130] From the viewpoint of photocurability, the photoinitiator
preferably comprises at least one of thioxanthones, acetophenones and
acyl phosphine oxides, or a mixture thereof. Of these, the photoinitiator
more preferably comprises a mixture of acetophenones and acyl phosphine
oxides.

[0131] The amount of the photoinitiator used is not particularly limited,
but is preferably within a range of from 0.5 to 10 parts by mass, and
more preferably within a range of from 1 to 5 parts by mass, per 100
parts by mass of the total amount of nonvolatile components in the active
energy ray-curable composition. The lower limit of the above range is
important to improve the curability with an active energy ray, and the
upper limit is important in terms of the cost and deep-section
curability.

[0132] The proportion of the silsesquioxane compound of the present
invention to a photoinitiator is not particularly limited, but the
photoinitiator is generally used in an amount of 1 to 20 parts by mass,
preferably 2 to 10 parts by mass, per 100 parts by mass of nonvolatile
components of the silsesquioxane compound.

Polymerizable Unsaturated Compound

[0133] The active energy ray-curable composition of the present invention
may further comprise a polymerizable unsaturated compound. There is no
particular limitation to the usable polymerizable unsaturated compounds,
as long as the polymerizable unsaturated compound is a compound other
than the silsesquioxane compound of the present invention and has at
least one polymerizable unsaturated double bond in its chemical
structure.

[0135] When used, the amount of the polymerizable unsaturated compound is
not particularly limited. However, from the viewpoint of the properties
of the formed coating film, the amount of the polymerizable unsaturated
compound used is preferably 0.1 to 1,000 parts by mass, and more
preferably 20 to 200 parts by mass, per 100 parts by mass of nonvolatile
components of the silsesquioxane compound of the present invention.

[0136] The active energy ray-curable composition of the present invention
may optionally comprise various additives, and may be diluted with a
solvent as required. Examples of the additives include sensitizers, UV
absorbers, light stabilizers, polymerization inhibitors, antioxidants,
defoaming agents, surface control agents, plasticizers, coloring agents,
and the like.

[0138] There is no particular limitation to the nonvolatile components in
the active energy ray-curable composition of the present invention. For
example, the amount is preferably 20 to 100 mass %, and more preferably
25 to 70 mass %. The above-mentioned amount range is important in terms
of the smoothness of the formed coating film, and to shorten the drying
time.

[0140] The substrates are not particularly limited. Specific examples of
the substrates include metal, ceramic, glass, plastic, wood, and the
like.

[0141] When a coating film is formed from the above-mentioned active
energy ray-curable composition, drying may be performed if required. The
drying method is not particularly limited insofar as the solvents
contained therein can be removed. For example, the drying may be
performed at a temperature of 20 to 100° C. for 3 to 20 minutes.

[0142] The film thickness of the coating film is arbitrarily adjusted
according to the purpose. For example, the film thickness is preferably 1
to 100 μm, and more preferably 1 to 20 μm. If the film thickness is
greater than the lower limit of the above-mentioned range, the coating
film will have excellent smoothness and appearance. If the film thickness
is below the upper limit of the above-mentioned range, the coating film
will have excellent curability and cracking resistance.

[0143] After the active energy ray-curable composition is applied to the
surface of a substrate, an active energy ray is irradiated to form a
cured coating film. There is no particular limitation to the radiation
source and radiation dose of the active energy-ray irradiation. Examples
of radiation sources of an active energy ray include an extra-high
pressure mercury-vapor lamp, a high pressure mercury-vapor lamp, a middle
pressure mercury-vapor lamp, a low-pressure mercury-vapor lamp, a
chemical lamp, a carbon arc light, a xenon light, a metal halide light, a
fluorescent light, a tungsten light, sunlight, and the like. The
radiation dose is, for example, preferably within a range of from 5 to
20,000 J/m2, and more preferably within a range of from 100 to
10,000 J/m2.

[0144] The active energy-ray irradiation can be performed in open air, or
in an inert gas atmosphere. Examples of inert gases include nitrogen,
carbon dioxide, and the like. From the viewpoint of curability, the
active energy-ray irradiation is preferably performed in an inert gas
atmosphere.

[0145] After the active energy-ray irradiation, the coating film may be
heated, if necessary. The heating can alleviate the deformation of the
coating film that is caused when the film is cured using the active
energy-ray irradiation. Further, the heating may improve the hardness and
adhesion of the coating film. The heating can generally be performed at
an ambient temperature of 150 to 250° C. for 1 to 30 minutes.

EXAMPLES

[0146] The present invention is described in more detail below with
reference to Examples. The phrases "parts" and "%" mean "parts by mass"
and "t by mass", respectively, unless otherwise stated. The structural
analysis and measurement in the Examples were conducted using, in
addition to the analysis equipment described above in the specification,
the following analysis equipment and measuring method.

29Si-NMR Analysis and 1H-NMR Analysis

[0147] Equipment: FT-NMR EX-400, manufactured by JEOL

[0148] Solvent: CDCl3

[0149] Internal standard substance: tetramethylsilane

FT-IR Analysis

[0150] Equipment: FT/IR-610, manufactured by JASCO Corporation

SP Value Measurement Method

[0151] The SP value used in the Examples is a solubility parameter that
can be measured by a simple measurement method (turbidimetric titration),
and the value is calculated according to the following formula suggested
by K. W. Suh and J. M. Corbett (see the description of Journal of Applied
Polymer Science, 12, 2359, 1968).

Formula: SP=( VmlδH+ VmhδD)/( Vml+ Vmh)

[0152] In turbidimetric titration, n-hexane is gradually added into a
solution of 0.5 g of a sample dissolved in 10 ml of acetone, and the
titration amount H (ml) at the turbidity point is read. Similarly,
deionized water is added into an acetone solution, and the titration
amount D (ml) at the turbidity point is read. These values are applied to
the following formulae to determine Vml, Vmh, δH, and δD. The
molecular volume (mol/ml) of each solvent is as follows: acetone: 74.4,
n-hexane: 130.3, and deionized water: 18. SP of each solvent is as
follows: acetone: 9.75, n-hexane: 7.24, and deionized water: 23.43.

Vml=74.4×130.3/((1-VH)×130.3+VH×74.4)

Vmh=74.4×18/((1-VD)×18+VD×74.4)

VH=H/(10+H)

VD=D/(10+D)

δH=9.75×10/(10+H)+7.24×H/(10+H)

δD=9.75×10/(10+D)+23.43×D/(10+D)

Example 1

[0153] One hundred parts of 3-isocyanatepropyltriethoxysilane, 47 parts of
2-hydroxyethyl acrylate, and 0.1 parts of methoquinone were placed in a
separable flask equipped with a reflux condenser, a thermometer, and a
stirrer, and the mixture was reacted at 100° C. for 12 hours while
blowing dry air thereinto. Thereby, a product (P1) was obtained.
Subsequently, 300 parts of toluene, 30 parts of a tetrabutylammonium
hydroxide 40% methanol solution, and 12 parts of deionized water were
placed in a separable flask equipped with a reflux condenser, a
thermometer, and a stirrer, and the mixture was cooled in an ice bath to
2° C. A solution containing a mixture of 300 parts of
tetrahydrofuran and 147 parts of the product (P1) was added thereto to
carry out a reaction at 20° C. for 24 hours. Then, volatile
components were removed by vacuum distillation, and the resulting product
was dissolved in 100 parts of propylene glycol monomethyl ether acetate.
Thereby, a product (P2) solution having a nonvolatile content of 50% was
obtained.

[0154] As a result of 29Si-NMR analysis of the product (P2), a peak
derived from a T3 structure in which all of three oxygen atoms attached
to Si were attached to other Si was observed at about -70 ppm, and a peak
derived from a T2 structure having a hydroxysilyl group was observed at
-59 ppm. The integrated intensity ratio of these peaks, i.e., the peak
derived from the T3 structure/the peak derived from T2 structure, was
90/10.

[0155] Further, as a result of 1H-NMR analysis of the product (P2), a
peak derived from a methylene group attached to Si was observed at 0.6
ppm. In addition, peaks derived from the carbon-carbon unsaturated bond
of an acryloyloxy group were observed at 5.9 ppm, 6.1 ppm, and 6.4 ppm.
Calculations based on the intensity ratio of these peaks showed that the
molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy
group to the methylene group attached to Si was 1.01.

[0156] As a result of FT-IR analysis of the product (P2), a peak belonging
to a urethane bond was observed at about 1540 cm-1.

[0157] Further, as a result of gel permeation chromatography (GPC)
analysis of the product (P2), the weight average molecular weight was
2,500.

[0158] The results of the 29Si-NMR, 1H-NMR, FT-IR, and GPC
analyses of the product (P2) demonstrated that the product (P2) was a
silsesquioxane compound comprising organic groups each directly attached
to a silicon atom, each of the organic groups being represented by
Formula (XXVI):

##STR00028##

wherein the silsesquioxane compound comprises 85% or more of a
silsesquioxane compound that has a weight average molecular weight of
2,500 and a structure in which all of the Si--OH groups are hydrolyzed
and condensed. The obtained silsesquioxane compound had an SP value of
10.5.

Example 2

[0159] One hundred parts of 3-isocyanatepropyltriethoxysilane, 58 parts of
4-hydroxybutylacrylate, and 0.1 parts of methoquinone were placed in a
separable flask equipped with a reflux condenser, a thermometer, and a
stirrer, and the mixture was reacted at 100° C. for 12 hours while
blowing dry air thereinto. Thereby, a product (P3) was obtained.
Subsequently, 1,000 parts of toluene, 20 parts of deionized water, 147
parts of the product (P3), and 10 parts of a 1N-aqueous hydrochloric acid
solution were placed in a separable flask equipped with a reflux
condenser, a thermometer, and a stirrer, and the mixture was heated to
60° C. After a reaction was allowed to proceed for 6 hours, the
reflux condenser was removed while a water recovery device was installed.
Then, water was distilled off while toluene was refluxed at 110°
C. After water removal was completed, the toluene was distilled off so
that the nonvolatile content in the resulting product was 50%. Thereby, a
product (P4) solution having a nonvolatile content of 50% was obtained.

[0160] As a result of 29Si-NMR analysis of the product (P4), a peak
derived from a T3 structure in which all of three oxygen atoms attached
to Si were attached to other Si was observed at about -70 ppm, and a peak
derived from a T2 structure having a hydroxysilyl group was observed at
-59 ppm. The integrated intensity ratio of these peaks, i.e., the peak
derived from the T3 structure/the peak derived from T2 structure, was
80/20.

[0161] Further, as a result of 1H-NMR analysis of the product (P4), a
peak derived from a methylene group attached to Si was observed at 0.6
ppm. In addition, peaks derived from the carbon-carbon unsaturated bond
of an acryloyloxy group were observed at 5.9 ppm, 6.1 ppm, and 6.4 ppm.
Calculations based on the intensity ratio of these peaks showed that the
molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy
group to the methylene group attached to Si was 1.02.

[0162] As a result of FT-IR analysis of the product (P4), a peak belonging
to a urethane bond was observed at about 1540 cm1.

[0163] Further, as a result of GPC analysis of the product (P4), the
weight average molecular weight was 3,000.

[0164] The results of the 29Si-NMR, 1H-NMR, FT-IR, and GPC
analyses of the product (P4) demonstrated that the product (P4) was a
silsesquioxane compound comprising organic groups each directly attached
to a silicon atom, each of the organic groups being represented by
Formula (XXVII):

##STR00029##

wherein the silsesquioxane compound comprises 55% or more of a
silsesquioxane compound that has a weight average molecular weight of
3,000 and a structure in which all of the Si--OH groups are hydrolyzed
and condensed. The obtained silsesquioxane compound had an SP value of
10.4.

Example 3

[0165] One hundred parts of Glycidyl POSS Cage Mixture (trade name,
manufactured by Hybrid Plastics) and 140 parts of butyl acetate were
placed in a separable flask equipped with a reflux condenser, a
thermometer, an air-introducing pipe, and a stirrer, and the mixture was
stirred at 60° C. until dissolution was complete. Then, 40 parts
of acetic acid, 0.5 parts of methoquinone, and 10 parts of
tetrabutylammonium bromide were added thereto to carry out a reaction at
120° C. for 12 hours while blowing dry air thereinto. The
thus-obtained reaction product was cooled to 80° C., and then, 85
parts of 2-isocyanate ethyl acrylate and 133 parts of butyl acetate were
added thereto to carry out a reaction at 80° C. for 10 hours.
Thereby, a product (P5) solution having a nonvolatile content of 50% was
obtained.

[0166] The Glycidyl-POSS Cage Mixture used as a starting material was
3-glycidoxypropyl group-containing cage-type polysilsesquioxane having a
weight average molecular weight of 1,800, and an epoxy equivalent of 168
g/eq.

[0167] As a result of 29Si-NMR analysis of the product (P5), only a
peak derived from a T3 structure in which all of three oxygen atoms
attached to Si were attached to other Si was observed at around -70 ppm,
while no peak derived from a T1 or T2 structure indicating the presence
of a hydroxysilyl group was observed.

[0168] Further, as a result of 1H-NMR analysis of the product (P5), a
peak derived from a methylene group attached to Si was observed at 0.6
ppm. In addition, peaks derived from the carbon-carbon unsaturated bond
of an acryloyloxy group were observed at 5.9 ppm, 6.1 ppm, and 6.4 ppm.
Calculations based on the intensity ratio of these peaks showed that the
molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy
group to the methylene group attached to Si was 1.00. A peak belonging to
an epoxy group was not observed. The epoxy equivalent determined by
titration was 10,000 g/eq or more.

[0169] Moreover, as a result of FT-IR analysis of the product (P5), a
broad peak belonging to a urethane bond, which was not observed in the
Glycidyl POSS Cage Mixture (starting material), was observed at around
1540 cm-1.

[0170] Further, as a result of GPC analysis of the product (P5), the
weight average molecular weight was 4,000.

[0171] The results of the 29Si-NMR, 1H-NMR, FT-IR, and GPC
analyses of the product (P5) demonstrated that the product (P5) was a
silsesquioxane compound comprising organic groups each directly attached
to a silicon atom, each of the organic groups being represented by
Formula (XXVIII):

##STR00030##

wherein the silsesquioxane compound comprises 55% or more of a
silsesquioxane compound that has a weight average molecular weight of
4,000 and a structure in which all of the Si--OH groups are hydrolyzed
and condensed. The obtained silsesquioxane compound had an SP value of
11.2.

Example 4

[0172] Four hundred parts of Epoxycyclohexyl-POSS Cage Mixture (trade
name, manufactured by Hybrid Plastics) and 600 parts of propylene glycol
monomethyl ether acetate were placed in a separable flask equipped with a
reflux condenser, a thermometer, an air-introducing tube, and a stirrer,
and the mixture was stirred at 60° C. until dissolution was
complete. Then, 136 parts of acetic acid, 1.5 parts of methoquinone, and
10 parts of tetrabutylammonium bromide were added thereto to carry out a
reaction at 120° C. for 24 hours while blowing dry air thereinto.
The thus-obtained reaction product was cooled to 80° C., and then,
318 parts of 2-isocyanate ethyl acrylate and 440 parts of butyl acetate
were added thereto to carry out a reaction at 80° C. for 10 hours.
Thereby, a product (P6) solution having a nonvolatile content of 50% was
obtained.

[0173] The Epoxycyclohexyl-POSS Cage Mixture used as a starting material
was 2-(3,4-epoxycyclohexyl)ethyl group-containing cage-type
polysilsesquioxane having a weight average molecular weight of 2,200 and
an epoxy equivalent of 178 g/eq.

[0174] As a result of 29Si-NMR analysis of the product (P6), only a
peak derived from a T3 structure in which all of three oxygen atoms
attached to Si were attached to other Si was observed at around -70 ppm,
while no peak derived from a T1 or T2 structure indicating the presence
of a hydroxysilyl group was observed.

[0175] Further, as a result of 1H-NMR analysis of the product (P6), a
peak derived from a methylene group attached to Si was observed at 0.6
ppm. In addition, peaks derived from the carbon-carbon unsaturated bond
of an acryloyloxy group were observed at 5.9 ppm, 6.1 ppm, and 6.4 ppm.
Calculations based on the intensity ratio of these peaks showed that the
molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy
group to the methylene group attached to Si was 1.00. A peak belonging to
an epoxy group was not observed. The epoxy equivalent was 10,000 g/eq or
more.

[0176] As a result of FT-IR analysis of the product (P6), a broad peak
belonging to a urethane bond, which was not observed in the
Epoxycyclohexyl-POSS Cage Mixture (starting material), was observed at
1540 am-1.

[0177] Further, as a result of GPC analysis of the product (P6), the
weight average molecular weight was 4,500.

[0178] The results of the 29Si-NMR, 1H-NMR, FT-IR, and GPC
analyses of the product (P6) demonstrated that the product (P6) was a
silsesquioxane compound comprising organic groups each directly attached
to a silicon atom, each of the organic groups being represented by
Formula (XXIX):

##STR00031##

wherein the silsesquioxane compound comprises 55% or more of a
silsesquioxane compound that has a weight average molecular weight of
4,500 and a structure in which all of the Si--OH groups are hydrolyzed
and condensed. The obtained silsesquioxane compound had an SP value of
10.6.

Example 5

[0179] Five hundred and sixty five parts of
3-glycidoxypropyltrimethoxysilane, 2,260 parts of 2-propanol, 2.0 parts
of tetrabutylammonium fluoride, and 65 parts of deionized water were
placed in a separable flask equipped with a reflux condenser, a
thermometer, and a stirrer, and the mixture was heated to 60° C.
by a mantle heater while being stirred under a nitrogen stream. After a
reaction was allowed to proceed for 10 hours at 60° C., the water,
methanol and 2-propanol were removed by vacuum distillation. Then, 600
parts of propylene glycol monomethyl ether acetate was added to the
resulting product to thereby obtain a product (P7) solution having a
nonvolatile content of 40%.

[0180] Subsequently, 1,000 parts of the product (P7) solution having a
nonvolatile content of 40%, 160 parts of acetic acid, 1.5 parts of
methoquinone, and 10 parts of tetrabutylammonium bromide were placed in a
separable flask equipped with a reflux condenser, a thermometer, and a
stirrer, and the mixture was reacted at 100° C. for 24 hours while
blowing dry air thereinto. The resulting product was cooled to 80°
C., and then, 170 parts of 2-isocyanate ethyl acrylate was added thereto.
The resulting mixture was allowed, as is, to undergo a reaction for 10
hours, and the reaction product was diluted with 210 parts of propylene
glycol monomethyl ether acetate. Thereby, a product (P8) solution having
a nonvolatile content of 50% was obtained.

[0181] As a result of 29Si-NMR analysis of the product (P7), only a
peak derived from a T3 structure in which all of three oxygen atoms
attached to Si were attached to other Si was observed at around -70 ppm,
while no peak derived from a T1 or T2 structure indicating the presence
of a hydroxysilyl group was observed.

[0182] Further, as a result of 1H-NMR analysis of the product (P7), a
peak derived from a methylene group attached to Si was observed at 0.6
ppm, and peaks derived from an epoxy group were observed at 2.6 ppm, 2.8
ppm, and 3.1 ppm. The molar ratio of the epoxy group to Si determined
from the ratio of these peaks was 1.0.

[0183] Moreover, as a result of FT-IR analysis of the product (P7), peaks
belonging to an Si--O--Si bond were observed at around 1,100 cm-1
and around 1,050 cm-1. However, almost no peak belonging to the
hydroxysilyl group was observed at around 3,500 cm-1. A peak
belonging to the epoxy group was observed at around 910 cm-1. The
epoxy equivalent of the product (P7) was 168 g/eq.

[0184] Furthermore, as a result of GPC analysis of the product (P7), peaks
each having a polystyrene equivalent molecular weight of 2,800, 2,000, or
1,200 were observed. Among these, the largest and sharpest peak having a
molecular weight of 1,200 was estimated to belong to an octamer, i.e., a
silsesquioxane compound [(RSiO3/2)8], and the proportion of
this component was 70 mass % of the whole. The weight average molecular
weight of the product (P7) was 1,750.

[0185] The results of the 29Si-NMR, 1H-NMR, FT-IR, and GPC
analyses of the product (P7) demonstrated that the product (P7) was a
silsesquioxane compound having a weight average molecular weight of 1,750
and comprising 70 mass % or more of a silsesquioxane compound represented
by the formula: (R7SiO3/2)8, wherein R7 is a
3-glycidoxypropyl group.

[0186] Subsequently, as a result of 29Si-NMR analysis of the product
(P8), only a peak belonging to the T3 structure was observed at around
-70 ppm.

[0187] Further, as a result of 1H-NMR analysis of the product (P8), a
peak derived from a methylene group attached to Si was observed at 0.6
ppm. In addition, peaks derived from the carbon-carbon unsaturated bond
of an acryloyloxy group were observed at 5.9 ppm, 6.1 ppm, and 6.4 ppm.
Calculations based on the intensity ratio of these peaks showed that the
molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy
group to the methylene group attached to Si was 0.50. The peak derived
from the epoxy group that was observed in the analysis of the product
(P7) disappeared. The epoxy equivalent was 10,000 g/eq or more, and the
NCO value was 0.

[0188] Moreover, as a result of FT-IR analysis of the product (P8), a
broad peak belonging to a hydroxyl group, which was not observed in the
analysis of the product (P7), was observed at around 3500 am-1, and
a broad peak belonging to a urethane bond was observed at around 1540
cm-1

[0189] Furthermore, as a result of GPC analysis of the product (P8), the
weight average molecular weight was 3,600.

[0190] The results of the 29Si-NMR, 1H-NMR, FT-IR, and GPC
analyses of the product (P8) demonstrated that the product (P8) was a
silsesquioxane compound comprising organic groups, each directly attached
to a silicon atom, 50 mol % of the organic groups being represented by
Formula (XXVIII), and 50 mol % of the organic groups being represented by
Formula (XXX),

##STR00032##

wherein the silsesquioxane compound comprises 70% or more of a
silsesquioxane compound that has a weight average molecular weight of
3,600 and a structure in which all of the Si--OH groups are hydrolyzed
and condensed. The obtained silsesquioxane compound had an SP value of
11.7.

Comparative Example 1

[0191] Three hundred parts of toluene, 30 parts of a tetrabutylammonium
hydroxide 40% methanol solution, and 12 parts of deionized water were
placed in a separable flask equipped with a reflux condenser, a
thermometer, and a stirrer, and the mixture was cooled in an ice bath to
2° C. Then, 110 parts of 3-acryloyloxypropyl trimethoxysilane
diluted with 300 parts of tetrahydrofuran was added thereto to carry out
a reaction at 20° C. for 24 hours. After volatile components were
removed by vacuum distillation, the resulting product was dissolved in
100 parts of propylene glycol monomethyl ether acetate. Thereby, a
product (P9) solution having a nonvolatile content of 50% was obtained.

[0192] As a result of 29Si-NMR analysis of the product (P9), a peak
derived from a T3 structure in which all of three oxygen atoms attached
to Si were attached to other Si was observed at around -70 ppm, and a
peak derived from a T2 structure having a hydroxysilyl group was observed
at -59 ppm. The integrated intensity ratio of these peaks, i.e., the peak
derived from the T3 structure/the peak derived from T2 structure, was
90/10.

[0193] Further, as a result of 1H-NMR analysis of the product (P9), a
peak derived from a methylene group attached to Si was observed at 0.6
ppm. In addition, peaks derived from the carbon-carbon unsaturated bond
of an acryloyloxy group were observed at 5.9 ppm, 6.1 ppm, and 6.4 ppm.
Calculations based on the intensity ratio of these peaks showed that the
molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy
group to the methylene group attached to Si was 1.00.

[0194] Furthermore, as a result of GPC analysis of the product (P9), the
weight average molecular weight was 1,500.

[0195] The results of the 29Si-NMR, 1H-NMR, FT-IR, and GPC
analyses of the product (P9) demonstrated that the product (P9) was a
silsesquioxane compound comprising organic groups each directly attached
to a silicon atom, each of the organic groups being represented by
Formula (XXXI):

##STR00033##

wherein the silsesquioxane compound comprises 80% or more of a
silsesquioxane compound that has a weight average molecular weight of
1,500 and a structure in which all of the Si--OH groups are hydrolyzed
and condensed. The obtained silsesquioxane compound had an SP value of
9.5.

Example 6

[0196] The product (P2) solution having a nonvolatile content of 50%
obtained in Example 1 and a polymerizable unsaturated compound (A1),
described later, were mixed so that the mass ratio of the product (P2) to
the polymerizable unsaturated compound (A1) was 1:1, and the mixture was
stirred at 40° C. for 24 hours to obtain a mixed solution. The
mixed solution was assessed to evaluate the compatibility of the product
(P2) obtained in Example 1 with the polymerizable unsaturated compound in
a solution state. The dissolved state of the mixed solution was visually
observed, and evaluated according to the following criteria. Table 1
shows the evaluation results.

[0197] Additionally, the product (P2) was mixed with each of polymerizable
unsaturated compounds (A2) to (A8), described later, to obtain mixed
solutions in the same manner as described above. Then, the compatibility
of each mixed solution was evaluated according to the same criteria as
above. Table 1 shows the evaluation results.

Determination of Compatibility

[0198] A: Homogeneous, transparent; good compatibility

[0199] B: Slightly cloudy or flickers when shaken; poor compatibility

[0200] C: Obviously cloudy, or at least one of separation, aggregation,
sedimentation, and gelation was observed; bad compatibility

[0209] The compatibility of each of the products (P4, P5, P6, P8, and P9)
obtained in Examples 2 to 5 and Comparative Example 1, respectively, with
each of the polymerizable unsaturated compounds was evaluated in a
solution state, in the same manner as in Example 6. Table 1 shows the
evaluation results.

TABLE-US-00001
TABLE 1
Polymerizable unsaturated compound
A1 A2 A3 A4 A5 A6 A7 A8
Ex. 6 Product (P2) A A A A A A A A
Ex. 7 Product (P4) A A A A A A A A
Ex. 8 Product (P5) A A A A A A A A
Ex. 9 Product (P6) A A A A A A A A
Ex. 10 Product (P8) A A A A A A A A
Comp. Product (P9) A B C B B B B C
Ex. 2

Example 11

[0210] Using active energy ray-curable compositions comprising the
silsesquioxane compounds of the present invention, the compatibility of
each product with each of the polymerizable unsaturated compounds was
evaluated. The test procedure is described below.

[0211] The product (P2) solution having a nonvolatile content of 50% (100
parts) obtained in Example 1, 50 parts of the polymerizable unsaturated
compound (A1), 3.0 parts of 1-hydroxy-cyclohexyl-phenyl-ketone
(photoinitiator), and 0.5 parts of
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (photoinitiator) were
mixed. The mixture was diluted with ethyl acetate to a nonvolatile
content of 30%, followed by stirring, thereby preparing an active energy
ray-curable composition.

[0212] Then, the active energy ray-curable composition was applied on an
intermediate plate (Note 1) to a film thickness of 10 μm (when dried)
using an applicator, and dried at 80° C. for 10 minutes to remove
the solvent. Subsequently, using a high-pressure mercury vapor lamp (80
W/cm), the coating film was cured by irradiation with UV light (peak top
wavelength: 365 nm) at a radiation dose of 2,000 mJ/cm2. The
appearance of the cured coating film was visually observed, and the
dissolved state was evaluated according to the following criteria. Table
4 shows the evaluation results.

[0213] Additionally, using the same formulation as above except that each
of the polymerizable unsaturated compounds (A2) to (A8) was used in place
of the polymerizable unsaturated compound (A1), active energy ray-curable
compositions each comprising one of the polymerizable unsaturated
compounds (A2) to (A8) were prepared. Then, coating films cured under the
same conditions as above were prepared. The coating films were visually
observed, and the dissolved state was evaluated according to the
following criteria. Table 2 shows the evaluation results.

[0214] (Note 1) Intermediate plate: ELECRON GT-10 (trade name,
manufactured by Kansai Paint Co., Ltd.; a cationic electrodeposition
coating composition) was applied by electrodeposition to a cold rolled
steel plate (0.8×150×70 mm) treated using Palbond #3020
(trade name, manufactured by Nihon Parkerizing Co., Ltd.; a zinc
phosphate treating agent) to a film thickness of 20 μm, and baked and
dried at 170° C. for 30 minutes to form an electrodeposition
coating film. The electrodeposition coating film was spray-coated with
WP-300 (trade name, manufactured by Kansai Paint Co., Ltd.; an aqueous
intermediate coating composition) to a cured film thickness of 25 μm,
and baked and dried in an electric hot air dryer at 140° C. for 30
minutes to prepare an intermediate plate.

Determination of Compatibility

[0215] A: Homogeneous, transparent; good compatibility

[0216] B: Slightly cloudy; poor compatibility

[0217] C: Obviously cloudy, or at least one of aggregation, seeding, and
crawling was observed; bad compatibility

Examples 12 to 15 and Comparative Example 3

[0218] Active energy ray-curable compositions were prepared in the same
manner as in Example 11 except that each of the product solutions (P4,
P5, P6, P8, and P9) obtained in Examples 2 to 5 and Comparative Example 1
was used in place of the product (P2) solution having a nonvolatile
content of 50%. Subsequently, the active energy ray-curable compositions
were cured under the same conditions as in Example 11 to form coating
films, and the compatibility of each product with each polymerizable
unsaturated compound was evaluated. Table 2 shows the evaluation results.

TABLE-US-00002
TABLE 2
Polymerizable unsaturated compound
A1 A2 A3 A4 A5 A6 A7 A8
Ex. 11 Product (P2) A A A A A A A A
Ex. 12 Product (P4) A A A A A A A A
Ex. 13 Product (P5) A A A A A A A A
Ex. 14 Product (P6) A A A A A A A A
Ex. 15 Product (P8) A A A A A A A A
Comp. Product (P9) A C C C C C C C
Ex. 3

Examples 16 to 22

[0219] Active energy ray-curable compositions were prepared using the
formulations shown in Table 3 in the same manner as the method for
preparing active energy ray-curable compositions and the method for
preparing cured coating films in Example 11. Then, cured coating films
with a film thickness of 10 μm (when dried) were formed on
intermediate plates (Note 1) to obtain test panels. Each of the obtained
test panels was evaluated for scratch resistance and weather resistance.
Table 3 shows the evaluation results.

Scratch Resistance

[0220] Each of the coating films was rubbed against commercially available
steel wool (#0000), and the coating film was visually observed and
evaluated according to the following criteria.

[0221] A: No scratching, cracking, or peeling, or slight scratching but
satisfactory from a practical standpoint

[0222] B: Scratched

[0223] C: Cracked, peeled, significantly scratched, etc.

Weather Resistance

[0224] Each of the obtained test panels was subjected to a 1000-hour test
using a Sunshine Weather-O-Meter. Then, the coating film of the panel was
visually observed and evaluated according to the following criteria.

[0225] A: No abnormalities, or slightly blistered, discolored, change in
gloss, peeled, etc., but satisfactory from a practical standpoint